Manipulating Photoconduction in Supramolecular Networks for Solar-Driven Nitrate Conversion to Ammonia and Oxygen

For photoelectrodes to be used in practical catalytic applications, challenges exist in achieving the efficient production and transport of photogenerated charge-separated states. Analogous concepts in traditional inorganic photoelectrodes can be applied to their organic-polymer counterparts with improved charge-separation efficiencies. In this work, we develop photoconductive organic networks to form a high-performance photoelectrode for NO₃^- reduction to NH₃. In the integrated network, interfaces between the organic electron-donating photoconductor and electron-accepting catalyst can generate charge carriers efficiently upon illumination, leading to enhanced charge separation for photoelectrocatalysis. The photoelectrode network is capable of converting NO₃^- to NH₃ at an external quantum efficiency of 13%. By coupling with a BiVO₄ photoanode in tandem, the system reduces NO₃^- to NH₃ and oxidizes H₂O to O₂ simultaneously at Faradaic efficiencies of 95-98% with sustained photocurrents and production yields. Investigation of the photoconductive network by steady-state/time-resolved spectroscopies reveals the efficient generation and transport of free charge carriers in the photoelectrode, providing a basis for high photoelectrocatalytic performances.